WO2005054135A1 - Procede de production d'oxyde de titane, melange actif par photocatalyse, procede de fabrication de film d'oxyde de titane utilisant ces elements, procede de production d'article revetu d'oxyde de titane et article revetu d'oxyde de titane fabrique au moyen de ces elements et solution de fabrication de film d'oxyde de titan - Google Patents

Procede de production d'oxyde de titane, melange actif par photocatalyse, procede de fabrication de film d'oxyde de titane utilisant ces elements, procede de production d'article revetu d'oxyde de titane et article revetu d'oxyde de titane fabrique au moyen de ces elements et solution de fabrication de film d'oxyde de titan Download PDF

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WO2005054135A1
WO2005054135A1 PCT/JP2004/016231 JP2004016231W WO2005054135A1 WO 2005054135 A1 WO2005054135 A1 WO 2005054135A1 JP 2004016231 W JP2004016231 W JP 2004016231W WO 2005054135 A1 WO2005054135 A1 WO 2005054135A1
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Prior art keywords
titanium oxide
forming
titanium
aqueous solution
film
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PCT/JP2004/016231
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English (en)
Japanese (ja)
Inventor
Naoya Shigemoto
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Shikoku Research Institute Incorporated
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Priority to JP2005515886A priority Critical patent/JP4680064B2/ja
Publication of WO2005054135A1 publication Critical patent/WO2005054135A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides

Definitions

  • the present invention relates to a method for producing titanium oxide, a photocatalytically active mixture, a method for forming a titanium oxide film using the same, a method for producing a titanium oxide coating, a titanium oxide coating obtained therefrom, and The present invention relates to a solution for titanium oxide film formation used therefor.
  • titanium oxide diacid titanium: TiO 2
  • TiO 2 titanium oxide
  • nitrogen oxide which is one of the air pollutants contained in the exhaust gas of automobiles
  • the nitrogen is irradiated by sunlight or the like containing ultraviolet rays.
  • the oxidized product can be removed by oxidizing it to nitrate ions.
  • Titanium oxide naturally functions as a photocatalyst for decomposing volatile organic substances such as formaldehyde, which is one of the substances causing so-called sick house syndrome, and for decomposing oil components such as heavy oil.
  • titanium oxide receives the energy of ultraviolet light to promote a chemical reaction, only titanium oxide present on the surface of a material to be irradiated with ultraviolet light functions as a catalyst. [0006] Therefore, when titanium oxide is used as the photocatalyst, it is considered that titanium oxide should be provided only on the surface of the material.
  • a method for forming a titanium oxide film for kneading powdery titanium oxide with cement and sand to form a kneaded material for a surface layer and thereby forming a surface layer of 2 mm to 15 mm on an object is provided.
  • a method for forming a titanium oxide film for kneading powdery titanium oxide with cement and sand to form a kneaded material for a surface layer and thereby forming a surface layer of 2 mm to 15 mm on an object is provided.
  • titanium oxide particles are highly dispersed in water to form a titanium oxide-containing slurry, and the surface of an object is impregnated with the titanium oxide-containing slurry, and this is dried to obtain a titanium oxide-containing slurry.
  • a method of forming a film has been proposed (e.g., see Patent Document 2.) 0
  • an anatase dispersion obtained by dispersing an anatase fine particles modified with a peroxo group or the like for example, see Patent Reference 3
  • a solution for forming a titanic acid product in which the concentration of cations other than titanium ions, titanium-containing ions, and hydrogen in the solution is 1Z2 or less of the titanium concentration
  • a solution for forming a titanium oxide from which ammonium ions, chloride ions, and the like have been removed for example, see Patent Document 5).
  • an aqueous solution of titanic acid obtained by adding a hydrogen peroxide solution to a gel or sol containing titanium hydroxide is heated in the presence of the object to be coated, and a titanium oxide film is formed on the surface of the object to be coated.
  • a method for forming a titanium oxide film is also known (for example, see Patent Document 7 and Patent Document 8).
  • Patent Document 1 JP-A-9-268509 (page 2-3, FIG. 1)
  • Patent Document 2 JP-A-11 33413 (pages 2-4)
  • Patent Document 3 JP-A-10-67516 (page 2-3)
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2001-48538 (pages 2-4)
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2000-247639 (pages 2-3)
  • Patent Document 6 JP-A-9-71418 (page 2-3)
  • Patent Document 7 Japanese Patent Application Laid-Open No. 1-224220 (page 13)
  • Patent Document 8 JP-A-2001-97717 (pages 4-5)
  • the titanium oxide present inside the titanium oxide particles does not function as a photocatalyst, and There is a problem that a part of titanium is wasted. Also, in this case, it was difficult to highly disperse titanium oxide on the surface of the object to be coated using titanium oxide powder. That is, the titanium oxide powder is formed of particulate titanium oxide, but a technique for producing a stable dispersion with very fine particles requires a high level of technology. Therefore, it is difficult to obtain a dense and well-adhered titanium oxide film. A large amount of titanium oxide is required for adjusting the above-mentioned kneaded material for surface layer or slurry containing titanium oxide. I will. For this reason, there has been a problem that the manufacturing cost increases.
  • Patent Documents 7 and 8 require thermal energy in order to thermally decompose a titanium peroxide compound considered to be a peroxotitanate ion into titanium oxide. Therefore, a large amount of heat energy is required depending on the shape of the object to be coated. Further, there is a problem that it is difficult to form a titanium oxide film on a material or an existing structure that cannot be heated. Then, when the titanium peroxide compound is thermally decomposed into titanium oxide, there is a risk that the titanium oxide aggregates and particles are generated, or that the titanium oxide is formed on the wall surface of the reaction vessel. In some cases, it will precipitate. Therefore, there has been a problem that extra titanium oxide is required, resulting in an increase in manufacturing cost.
  • the present invention has been made to solve such a conventional problem, and an acid capable of reducing the amount of titanium oxide to be used and capable of forming a film by a simple process.
  • the purpose of the present invention is to provide a method for forming a titanium film. This aims at reducing the production cost of the titanium oxide coated body.
  • the present inventor has conducted intensive studies in order to solve the above-mentioned problems, and as a result, has found that titanium oxide is produced by a simple process of reacting peroxotitanate ion with alkali.
  • fine particles of titanium oxide can be precipitated, and if this reaction is used to precipitate titanium oxide on the surface of a film-forming target, it functions as a photocatalyst. It has been found that it is possible to provide a thin film state or a highly dispersed titanium oxide film exposed on the surface to a sufficient extent.
  • the titanium oxide thus produced was identified as titanium dioxide having an X-ray diffraction pattern force, and this amorphous titanium oxide was also identified. Was confirmed to be involved in the photocatalytic function.
  • salts insoluble in water such as alkaline earth metal sulfates are formed as by-products, and these hardly soluble salts are formed with titanium dioxide and titanium dioxide. Without separation, it was confirmed that in the state in which these hardly soluble salts were mixed, the titanium dioxide had a function as a photocatalyst.
  • the peroxotitanate ion is a force that can be used in the form of a peroxotitanate ion aqueous solution.
  • a titanium salt aqueous solution and hydrogen peroxide are mixed, the peroxotitanate ion is generated.
  • the peroxotitanate ion it was found that either of (1) the form of an aqueous solution of peroxotitanate ion and (2) the combined use of an aqueous solution of a titanium salt and hydrogen peroxide are usable.
  • an alkali and (1) an aqueous solution of peroxotitanate ion or (2) an aqueous solution of a titanium salt and hydrogen peroxide are used, even if these chemicals are applied to the object to be treated, they are sequentially treated.
  • a thin film of titanium oxide can be similarly applied to a film-forming target.
  • the alkali is applied to the object to be film-formed, and then the aqueous solution is mixed with (1) an aqueous solution of peroxotitanate ion or (2) an aqueous solution of a titanium salt.
  • the surface of the object to be film-formed is uniformly wetted with alkali by applying the hydrogen peroxide, (1) an aqueous solution of peroxotitanate ion or (2) an aqueous solution of a titanium salt and hydrogen peroxide are sprayed.
  • a highly-dispersed titanium oxide film can be obtained.
  • the alkali may be applied later. This makes it possible to obtain a highly dispersed titanium oxide film by spraying an alkaline aqueous solution after the perotasotitanate ion is uniformly applied to the surface of the object.
  • an alkali originally contained in a film-forming target can be used as it is.
  • a typical example of such a film formation target is a hydraulic inorganic material (for example, a cement material) using calcium hydroxide as a hardening source.
  • a hydraulic inorganic material for example, a cement material
  • calcium hydroxide as a hardening source.
  • an alkali may be additionally provided to the film formation target.
  • the state of the titanium oxide film to be formed can be grasped.
  • an aqueous alkali solution may be additionally sprayed. Therefore, the alkali in the present invention may be initially present or may be applied later.
  • the desired titanium oxide film can be formed by reacting with peroxotitanate ions.
  • the invention described in claim 1 of the present application is characterized in that a peroxotitanate ion, which may be derived from a reaction product of an aqueous solution of a titanium salt and hydrogen peroxide, is allowed to act in the presence of an alkali. Is a manufacturing method.
  • the titanium oxide thus obtained is a noncrystalline amorphous titanium dioxide and has activity as a photocatalyst.
  • the invention according to claim 2 is characterized in that a peroxotitanate ion, which may be derived from a reaction product between an aqueous solution of a titanium salt and hydrogen peroxide, is allowed to act in the presence of an alkali. And a photocatalytically active mixture.
  • a peroxotitanate ion which may be derived from a reaction product between an aqueous solution of a titanium salt and hydrogen peroxide
  • a photocatalytically active mixture is added to titanium oxide.
  • a mixture containing a side reaction product can be used as it is as a photocatalytically active mixture.
  • Such by-products include salts that are hardly soluble in water.
  • a sulfate mixture of a hardly soluble alkaline earth metal precipitates simultaneously with titanium dioxide, The mixture functions as a photocatalyst, and the alkaline earth metal sulfate mixture functions as a binder between titanium oxide or titanium oxide and another substance (for example, an object to be formed).
  • the photocatalytically active mixture is essentially formed into particles mainly composed of titanium oxide, it can be used as a dispersed or redispersed slurry, for example.
  • the invention according to claim 3 is characterized in that peroxotitanate ion, which may be derived from a reaction product of an aqueous solution of a titanium salt and hydrogen peroxide, is allowed to act in the presence of an alkali. This is a method for forming a titanium film.
  • the peroxytitanate ion and the alkali act to form a titanium oxide film with high dispersion on the surface of the film formation target.
  • a highly dispersed titanium oxide film can be formed, so that the amount of titanium oxide used can be reduced.
  • film formation can be performed by a simple process, manufacturing costs can be reduced.
  • the peroxotitanate ion is (1) provided to the film-forming target in the form of an aqueous solution, or (2) an aqueous solution of titanium salt and hydrogen peroxide.
  • the peroxotitanate ion is (1) provided to the film-forming target in the form of an aqueous solution, or (2) a titanium salt aqueous solution and hydrogen peroxide are applied to the film-forming target.
  • a titanium oxide film can be formed using a perotasotitanate ion generated by the action of a titanium salt and hydrogen peroxide.
  • the invention according to claim 5 is the titanium oxide film according to claim 4, wherein the alkali is derived from an object to be formed and is given to Z or the object to be formed. This is the film forming method.
  • the step of applying alkali can be omitted, the amount of alkali applied can be reduced, and the titanium oxide film can be formed even on a surface that does not exhibit alkali. it can.
  • titanium oxide is deposited on the surface of the film-forming target, so that a highly dispersed titanium oxide film is easily formed. Is provided.
  • the film formation target is a microporous porous material, the titanium oxide film can be reliably provided on the surface or in the micropores near the surface.
  • the invention according to claim 7 is characterized in that an aqueous solution of peroxotitanate ion is applied to the object to be formed, and then an aqueous solution of alkali is applied. This is a film forming method.
  • the object to be formed has an affinity for the aqueous solution of peroxotitanate ion.
  • the peroxotitanate ion aqueous solution is easily applied uniformly (highly dispersed) to the object to be formed, and a highly dispersed titanium oxide film can be formed by the subsequent application of an alkali.
  • each of the titanium oxides may be used.
  • the film forming solution is reliably applied to the surface of the micropores, and the surface of the micropores is surely coated with titanium oxide.
  • a membrane can be provided.
  • the invention according to claim 8 is characterized in that, after applying a mixed solution of a titanium salt aqueous solution and hydrogen peroxide to the object to be formed, an alkaline aqueous solution is applied. This is a method for forming a titanium oxide film.
  • peroxotitanate ions generated by applying a mixed solution of a titanium salt aqueous solution and hydrogen peroxide to a film-forming target act on an alkali aqueous solution that is finally applied to form an acid.
  • a dani titanium film can be formed.
  • the first applied liquid is likely to be uniformly applied to the film-forming object (highly dispersed) and finally applied.
  • the alkali thus formed, a highly dispersed titanium oxide film can be formed.
  • each silicon oxide titanium can be used.
  • the solution for film formation is surely applied to the surface of the micropore, and the titanium oxide film can be surely applied to the surface of the micropore.
  • the invention according to claim 9 is characterized in that an aqueous solution of titanium salt is applied to the object to be film-formed, an aqueous solution of hydrogen peroxide is applied, and then an aqueous solution of alkali is applied. 5.
  • the aqueous solution of titanium salt applied first is easily applied uniformly to the object to be film-formed (highly dispersed), A highly dispersed oxidized titanium film can be formed by the action of the alkali imparted to the film.
  • each of the titanium oxides may be used.
  • the solution for film formation is surely applied to the surface of the micropore, and the titanium oxide film can be surely applied to the surface of the micropore.
  • the hydrogen peroxide solution to be applied first is likely to be uniformly applied to the object to be film-formed (high dispersion). ), And a highly dispersed oxidized titanium film can be formed by the application of the alkali finally applied.
  • each of the titanium oxides may be used.
  • the solution for film formation is surely applied to the surface of the micropore, and the titanium oxide film can be surely applied to the surface of the micropore.
  • the invention according to claim 12 is characterized in that an aqueous titanium salt solution, an aqueous hydrogen peroxide solution and an aqueous alkaline solution are simultaneously applied to the object to be formed, and the titanium oxide film according to claim 6 is formed. It is a membrane method.
  • the invention according to claim 13 is characterized in that an oxidized titanium film is formed by attaching an aqueous solution of peroxotitanate ion to a film-forming target having an alkali on the surface. This is a method for forming a titanium film.
  • peroxotitanic acid is added to a film-forming target having an alkali on its surface.
  • the alkali reacts with the peroxotitanate ion aqueous solution to generate titanium oxide (TiO 2), thereby forming a titanium oxide film.
  • an oxidized titanium film can be easily formed on the surface of a film formation target without requiring a heating step or an ion exchange step. .
  • titanium oxide can be easily highly dispersed as compared with the case of using a titanium oxide aqueous solution or a titanium oxide gel containing titanium oxide.
  • the amount of titanium oxide required for film formation can be reduced, and the manufacturing cost can be reduced.
  • the invention described in claim 14 is characterized in that the aqueous peroxotitanate ion solution is a mixed aqueous solution of a titanium salt aqueous solution and a hydrogen peroxide solution. This is a method for forming a titanium oxide film.
  • the aqueous peroxotitanate ion solution is a mixed aqueous solution of a titanium salt aqueous solution and a hydrogen peroxide solution, so that it can be easily obtained only by mixing the titanium salt aqueous solution and the hydrogen peroxide solution.
  • An aqueous peroxotitanate ion solution can be obtained.
  • a hydrogen peroxide solution is adhered to form a titanium oxide film. This is a method for forming a titanium oxide film.
  • the hydrogen peroxide solution is deposited.
  • peroxotitanate ions are generated by the titanium salt aqueous solution and the hydrogen peroxide solution. .
  • the peroxotitanate ion reacts with the alkali on the surface to generate titanium oxide, whereby a titanium oxide film can be formed on the surface of the film formation target.
  • a titanium oxide film in which titanium oxide is highly dispersed can be easily formed without requiring a heating step or an ion exchange step. Can be formed on the surface of the substrate.
  • the repelling force is different from the case where a titanium oxide aqueous solution containing titanium oxide or a titanium oxide gel is used. In comparison, it is possible to easily disperse the titanium oxide easily.
  • the titanium salt is titanium sulfate or titanium chloride, and the titanium oxide film according to claim 14 or 15 is formed. Is the way.
  • the titanium salt is titanium sulfate or titanium chloride
  • the titanium salt can be easily dissolved in water, and a titanium salt aqueous solution can be easily obtained.
  • the invention according to claim 17 is characterized in that the object to be film-formed is made of an alkali-containing material, and the titanium oxide film according to any one of claims 13 to 16 is formed. It is a film method.
  • the film-forming target is made of an alkali-containing material, a separate step of holding the alkali on the surface of the film-forming target is not required, and the formation of the titanium oxide film is not required. The number of film processes can be reduced.
  • the surface is formed of an alkali-containing material held on the film-forming object. It is a method of forming a titanium oxide film described in the section.
  • the object to be film-formed since the surface is formed of the alkali-containing material held on the object to be film-formed, the object to be film-formed has a property of hardly holding an alkali.
  • the titanium oxide film can be formed on the object to be formed via the alkali-containing material.
  • the invention according to claim 19 is the method according to claim 17 or 18, wherein the alkali-containing material is cement or fly ash. is there.
  • the alkali-containing material is cement or fly ash
  • the alkali-containing material is cement
  • a titanium oxide film can be easily formed on a structure or the like
  • the alkali-containing material is fly ash
  • a powder capable of decomposing organic substances such as oil mixed in soil or the like can be obtained.
  • the invention according to claim 21 is characterized in that the surface is made of a porous material, and the alkali is carried on the surface formed by the porous material. 17.
  • the object to be formed is a porous material. Therefore, if the titanium oxide film is formed toward the surface opening of the porous material, the titanium oxide The surface area of the membrane can be increased.
  • the surface also has a porous material strength, so that a large number of pores of the porous material can support the alkali.
  • the porous substance is concrete, silica gel.
  • the porous substance is one or a mixture of two or more of concrete, silica gel, alumina, talc, calcium carbonate, and sand. Adsorbs nitrogen oxides and bacteria when ultraviolet light is not irradiated, and oxidizes nitrogen oxides and bacteria by the photocatalytic function of the titanium oxide film when irradiated with ultraviolet light. Can be disassembled.
  • the invention described in claim 23 is characterized in that the alkali is any one of an alkali metal hydroxide, an alkaline earth metal hydroxide, and ammonia.
  • the titanium salt is titanium sulfate
  • the alkaline earth metal hydroxide is calcium hydroxide, strontium hydroxide, barium hydroxide, or any of the following.
  • the titanium salt is titanium sulfate
  • the alkaline earth metal hydroxide is any one of calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • Calcium sulfate, strontium sulfate or sulfur Barium acid is formed.
  • the calcium sulfate, strontium sulfate, or barium sulfate functions as a binder for titanium oxide (titanium dioxide) without substantially reducing the photocatalytic ability of the titanium oxide film.
  • the titanium salt is titanium chloride
  • the alkaline earth metal hydroxide is calcium hydroxide, strontium hydroxide, barium hydroxide! 24.
  • the titanium salt is titanium chloride and the alkaline earth metal hydroxide is any one of calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • the alkaline earth metal hydroxide is any one of calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • the titanium oxide film-forming solution containing peroxotitanate ions which is derived from a reaction product of the aqueous titanium salt solution and hydrogen peroxide, is formed in a spray form. 26.
  • the titanium oxide film-forming solution can be applied by any application method such as coating, dipping, or spraying. A more uniform and highly dispersed titanium oxide film can be formed.
  • the invention according to claim 27 is a method for producing a titanium oxide coating, characterized by using the method for forming a titanium oxide film according to any one of claims 3-26.
  • the invention according to claim 28 provides a titanium oxide coating obtained by the method for forming a titanium oxide film according to any one of claims 3-26 or the method for producing a titanium oxide coating according to claim 27. Body.
  • the invention according to claim 29 is a solution for titanium oxide film formation comprising a two-part liquid composed of an aqueous solution of peroxotitanate ion and an aqueous alkaline solution.
  • the invention according to claim 30 is an oxidized titanium film-forming solution which has a two-component power of a mixed solution of a titanium salt aqueous solution and hydrogen peroxide and an alkali solution.
  • the invention according to claim 31 is an oxidizing titanium film-forming solution comprising a three-part solution consisting of a titanium salt aqueous solution, a hydrogen peroxide solution, and an alkaline solution.
  • the present invention it is possible to produce a mixture that functions as a photocatalyst containing titanium oxide or titanium oxide by the action of peroxotitanate ions and an alkali.
  • An titanium oxide film can be formed on the surface of the object. According to the method for forming a titanium oxide film, the amount of titanium oxide used can be reduced, and the film can be formed by an easy process, whereby the manufacturing cost can be reduced.
  • an aqueous peroxotitanate ion solution is attached to a film formation target in the presence of an alkali. Reacts to form titanium oxide (TiO 2), which
  • a titanium film is formed.
  • a titanium salt aqueous solution is deposited in the presence of an alkali, and then a hydrogen peroxide solution is deposited.
  • Peroxotitanate ions are generated by the titanium salt aqueous solution and the hydrogen peroxide solution.
  • the peroxytitanate ion and the alkali react with each other to form titanium oxide, whereby a titanium oxide film can be formed on the surface of the object to be formed.
  • a titanium oxide film of the present invention since alkali and perotasotitanate ions are sequentially applied, deposition of titanium oxide is performed on the surface of the object to be formed. Therefore, it has a feature that a highly dispersed titanium oxide film is easily formed. Thus, for example, even when the film formation target is a microporous porous material, the titanium oxide film can be reliably applied to the surface or in the micropores near the surface.
  • alkali and peroxytitanate ions are simultaneously applied to a film-forming target, and thus can be applied in a single step. It can be simplified.
  • a titanium oxide film can be easily formed on the surface of a film formation target without a heating step or an ion exchange step. it can.
  • peroxotitanate ions are allowed to react in the presence of an alkali, the titanium oxide can be easily highly dispersed as compared with the case of using a titanium oxide aqueous solution or a titanium oxide gel containing titanium oxide. Can be.
  • FIG. 1 Relationship between H 2 O ZTi (molar ratio) of peroxotitanate ion aqueous solution and NO adsorption rate
  • FIG. 1 A first figure.
  • FIG. 1 A first figure.
  • FIG. 3 is a graph showing NO adsorption rates for various alkalis.
  • FIG. 4 is a graph showing NO photooxidation speed for each alkali.
  • FIG. 2 is a diagram showing the relationship between the 2 molar ratio) and the NO adsorption rate.
  • FIG. 2 is a diagram showing a relationship between (2 molar ratio) and the NO photooxidation speed.
  • FIG. 7 is a diagram showing an X-ray diffraction result of a precipitate formed by mixing an aqueous alkali solution and an aqueous solution of perotasotitanate ion.
  • An example of a preferred embodiment of the present invention is to form a film-forming object by allowing peroxotitanate ion, which may be derived from a reaction product of a titanium salt aqueous solution and hydrogen peroxide, to act in the presence of an alkali.
  • a titanium oxide film is formed by forming a titanium oxide film on the substrate.
  • the peroxytitanate ion and the alkali can act to easily disperse titanium oxide (TiO 2) on the surface of the object to be film-formed, thereby achieving low cost.
  • the titanium oxide film can be formed.
  • the peroxotitanate ion is applied to the film-forming target in the form of (1) an aqueous solution.
  • an aqueous solution either (2) the titanium salt aqueous solution and hydrogen peroxide are used in combination.
  • the titanium salt When applied in combination, the titanium salt may be applied separately to the film-forming target in the form of an aqueous solution of a titanium salt and hydrogen peroxide, respectively. It may be applied as one liquid in the form of a mixed liquid of an aqueous solution and hydrogen peroxide.
  • the titanium salt aqueous solution and hydrogen peroxide act to give peroxotitanate ions, and the peroxotitanate ions act with alkali to form a titanium oxide film that can be highly dispersed.
  • the titanium oxide film capable of being highly dispersed means that the titanium oxide particles are highly dispersed on the surface of the object to be coated. Since the particles of titanium oxide are highly dispersed on the surface of the object to be coated, when the surface of the object to be coated is irradiated with light, the titanium oxide formed on the surface is efficiently irradiated with light. Thus, it is possible to maximize the properties of titanium oxide as a photocatalyst.
  • the alkali used in the present invention may be derived from an object to be formed, or may be an alkali added later.
  • the step of applying alkali can be omitted or the amount of alkali applied can be reduced.
  • the alkali may be applied to the film-forming object.
  • a titanium film can be formed.
  • TiO 2 titanium oxide
  • the titanium oxide film can be formed on the surface of the object to be formed.
  • an aqueous solution of a soluble titanium salt is attached to a film-forming target having an alkali on its surface
  • an aqueous solution of hydrogen peroxide an aqueous solution of H2O
  • the peroxytitanate ion is generated by the aqueous solution of the soluble titanium salt and the aqueous solution of hydrogen peroxide since the aqueous solution of hydrogen peroxide is attached after the aqueous solution of the soluble titanium salt is attached. Then, the peroxotitanate ion reacts with the alkali on the surface to form titanium oxide, whereby a titanium oxide film can be formed on the surface of the film formation target.
  • the film formation target does not exhibit alkalinity, or exhibits alkalinity, the amount of alkali is reduced. If it is not enough, an alkali can be additionally provided. In such a case, the order of providing the alkali and peroxotitanate ions to the film formation target is not particularly limited.
  • a film-forming solution containing an alkali and a peroxotitanate ion may be applied to a film-forming target simultaneously or sequentially.
  • titanium oxide is deposited on the surface of the film-forming target, so that a highly dispersed titanium oxide film is easily formed. Is provided.
  • the film formation target is a microporous porous material, the titanium oxide film can be reliably provided on the surface or in the micropores near the surface.
  • a method for forming a titanium oxide film in which a film-forming solution containing peroxotitanate ions is sequentially applied to a film-forming object after a film-forming solution containing an alkali is applied.
  • the alkali to be applied first is easily applied uniformly to the film-forming target, and then the dispersion is highly dispersed by applying a film-forming solution containing peroxotitanate ion. Can be formed.
  • a titanium oxide film forming method in which a film forming solution containing peroxotitanate ions is applied to a film forming object and then a film forming solution containing an alkali is applied is performed.
  • a film forming solution containing an acid ion peroxytitanate ion is likely to be uniformly applied to a film-forming target, and then a highly dispersed acid is applied by applying an alkaline force.
  • a dani titanium film can be formed.
  • the titanium salt aqueous solution and the hydrogen peroxide may be applied to a film-forming target in the form of a mixed solution.
  • peroxotitanate ions generated in the mixed solution are subsequently applied.
  • the titanium oxide film can be formed by acting with an alkaline aqueous solution.
  • a hydrogen peroxide solution may be applied, and then the alkali aqueous solution may be applied.
  • the peroxotitanate ion generated by applying the peroxydani hydrogen water can act on the subsequently applied aqueous alkali solution to form an oxyditanium film.
  • aqueous solution of a titanium salt may be applied, and then an aqueous solution of an alkali may be applied.
  • Peroxytitanate ions generated by applying a hydrogen peroxide solution to a film-forming target and then applying an aqueous solution of a titanium salt act on an alkali aqueous solution to be applied thereafter to form an oxidized titanium film.
  • a peroxotitanate ion aqueous solution and an alkaline aqueous solution may be simultaneously applied to a film formation target.
  • Simultaneous application of a titanium oxide film-forming solution, which also has a two-component power of a peroxotitanate ion aqueous solution and an alkaline aqueous solution, to the object to be formed enables two solutions to be applied in a single step, thus simplifying the process. I can make it sharp.
  • a film-forming solution of titanium oxide which is composed of three liquids of a titanium salt aqueous solution, a hydrogen peroxide solution and an aqueous alkaline solution, may be simultaneously applied to the film-forming target.
  • a titanium salt solution, a hydrogen peroxide solution, and an alkaline aqueous solution may be simultaneously applied to the film-forming target.
  • a two-liquid titanium oxide film forming solution in which a mixed solution of a titanium salt aqueous solution and hydrogen peroxide is used as one solution and an alkali solution is used as another solution is applied simultaneously or sequentially. You can. Also in this case, the application step can be simplified if the application is performed simultaneously.
  • Such an oxidizing titanium film-forming solution can be applied by any application method such as coating, dipping, or spraying. Thus, a more uniform and highly dispersed titanium oxide film can be formed.
  • each titanium oxide film forming solution is stored in a chemical solution tank or the like, and is sprayed onto a film forming target using a spraying device having a plurality of spray holes corresponding to the number of the respective chemical solutions. What is necessary is just to spray a chemical solution toward it.
  • the sprayed chemicals are mixed with each other in the air, and titanium oxide precipitates in the air.
  • the film-forming target has a smooth surface or is porous, it has enough openings to allow the particulate titanium oxide to precipitate in the air. For example, a highly dispersed acid A titanium oxide film is formed.
  • titanium oxide is generated in the storage tank. In such a case, it becomes the same as the case of spraying particulate titanium oxide or the case of spraying gelled titanium oxide, and it becomes difficult to form a highly dispersed titanium oxide film.
  • the titanium oxide film can be easily formed on the surface of the film formation target without the necessity of the heating step and the ion exchange step.
  • a film can be formed, and a titanium oxide coating having titanium oxide highly dispersed on the surface can be produced.
  • the peroxytitanate ion is made to react with the alkali in the present invention, so that the aqueous solution containing titanium oxide and the titanium oxide gel containing titanium oxide are used.
  • the titanium oxide can be easily highly dispersed. Therefore, the amount of titanium oxide required for film formation can be reduced, and the manufacturing cost can be reduced.
  • the titanium oxide film in which the titanium oxide is highly dispersed has a large contact area with the decomposition target, so that the titanium oxide film is efficient, and can exhibit higher photocatalytic ability.
  • a predetermined substance is adsorbed when it is not irradiated with ultraviolet light, and the photocatalyst is adsorbed when it is irradiated with ultraviolet light. It is considered to function. For example, if a titanium oxide film formed by the film forming method of the present invention is provided outdoors, nitrogen oxide (NOx), one of the air pollutants, is adsorbed at night and sunlight is irradiated during the day. Then, it is considered that it functions as a photocatalyst to oxidize and remove the nitrogen oxide.
  • NOx nitrogen oxide
  • the present invention it is possible to impart a function of adsorbing and removing nitrogen oxides in the air to concrete products and various materials capable of holding alkalis, thereby contributing to purification of the air environment. Can be.
  • the dirt component mainly composed of organic matter attached to the surface of such concrete products and the like is decomposed by the titanium oxide film.
  • the aqueous solution of peroxotitanate ion used in the present invention is an aqueous solution containing peroxotitanate ion (peroxide titanate) derived from peroxotitanic acid (titanium peroxide: TiO ⁇ ).
  • the production method that can be used with a liquid is not particularly limited.
  • titanium sulfate (Ti (SO)) water Mix a solution or an aqueous solution of titanium salt such as an aqueous solution of titanium chloride (TiCl) with aqueous hydrogen peroxide.
  • titanium salt aqueous solution examples include potassium peroxotitanate (K TiO ⁇ 600) and sodium peroxotitanate in addition to titanium sulfate and titanium chloride.
  • an alkali metal hydroxide As the alkali used in the present invention, an alkali metal hydroxide, an alkaline earth metal hydroxide, and the like can be used.
  • sodium hydroxide (NaOH) sodium hydroxide
  • hydroxide Calcium (Ca (OH) hydroxide Calcium (Ca (OH)
  • strontium hydroxide (Sr (OH) strontium hydroxide
  • barium hydroxide (Ba (OH) barium hydroxide
  • ammonia (NH 2) or the like can be used as the alkali.
  • a titanium oxide film is formed by reacting an alkali with a peroxotitanate ion, thereby forming titanium oxide in a deep portion of a film formation target.
  • the titanium oxide film can be efficiently formed only on the surface to be smooth (or only on the surface layer). In other words, since titanium oxide exhibits a photocatalytic function when irradiated with ultraviolet light, if a titanium oxide film is formed on the surface of a film-forming target, a greater effect can be obtained using a small amount of titanium. .
  • the alkali may be held on the surface of the film formation target in any manner.
  • the material of the object to be film-formed may be formed of an alkali-containing material so that the surface thereof has alkali.
  • a separate alkali-containing material may be added to the object of film formation. It may be configured to be held so that its surface has alkali.
  • an alkali-containing liquid may be applied to a film-forming target, sprayed, dipped, or the like, so that alkali is attached to the surface.
  • a porous substance This is a glass in which an alkali is carried in pores of the porous material by spraying an alkali-containing liquid on the porous material.
  • a hydraulic inorganic material using calcium oxide CaO as a hardening source such as alkaline cement or fly ash
  • alkaline cement or fly ash may be used as the alkali-containing material.
  • Film formation of such an alkali-containing material When used as an object, it is possible to form a surface having an alkali that can be particularly processed without additional processing.
  • a powdery fly ash is used as a film-forming object to form an oxidized titanium film, the organic matter is decomposed and removed by spraying on soil or the like contaminated with organic matter such as oil and pesticides. It is thought that it can be done.
  • a separate alkali-containing material is held on the film-forming object, for example, a paste-like calcium hydroxide, strontium hydroxide, cement, etc. May be held by coating. Even in this case, the surface of the film formation target is formed by the retained alkali-containing material, and the surface has alkali.
  • an alkali-containing liquid is attached to the surface of a film-forming target
  • a method of attaching the alkali-containing liquid is not limited.
  • an aqueous solution of sodium hydroxide, an aqueous solution of barium hydroxide, or the like can be applied to the object to be film-formed, immersed, or sprayed to adhere.
  • it is applied by coating even an existing structure or the like can be easily attached.
  • any substance having a large number of fine pores can be arbitrarily selected within a range in which the effects of the present invention are exhibited.
  • concrete, silica gel, alumina, talc, sand, calcium carbonate, calcium nitride, calcium carbide, hydroxyapatite, etc. may be used, or a mixture of any two or more of these may be used.
  • the porous substance is not an organic substance. This is because the porous substance itself may be decomposed due to the photocatalytic function of titanium oxide formed on the surface.
  • an organic material made of an organic substance is used as a film-forming object (base), for example, the above-described organic material may be used to hold an inorganic substance as an intermediate layer, and the surface may be formed with the inorganic substance. .
  • the titanium oxide film can be formed on the organic material as the base material, and the amount of the organic material decomposed by the photocatalytic function of the titanium oxide can be reduced. .
  • the method for attaching the hydrogen oxide water is not particularly limited, and it can be attached by a desired method such as spraying, coating, and dipping. Spraying onto a film-forming object by spraying makes it possible to adhere more uniformly and highly dispersed. In addition, if it is applied by coating, even an existing structure can be easily attached. Further, for example, in the case of attaching to a concrete block or the like at the production stage, from the viewpoint of production efficiency, attachment by immersion is preferable.
  • the amorphous dioxide titanium obtained according to the present invention precipitates in the form of fine particles, so that in addition to its use as a film, it can be used in a slurry state by utilizing the function as fine particles as it is.
  • the titanium thin film can be provided by mixing the slurry with an appropriate binder or by directly applying the slurry to an object.
  • the above-mentioned target for film formation can be used as it is, but the application to the porous body having fine pores is more easily performed by the above-described film formation method than in the case of using a slurry.
  • the reaction mixture containing titanium oxide obtained by the reaction of the present invention has a feature that it functions as a photocatalyst in the form of a mixture as it is. This eliminates the need to separate and purify the titanium oxide produced according to the present invention before use.
  • separation and purification is possible, including when all of the side reaction products are soluble, or when separation and purification is easy, etc., it is possible to use titanium dioxide after separation and purification. It goes without saying that it is good.
  • Sample 1 and Sample 36 were manufactured according to Examples 1 to 5 and Comparative Examples 1 and 2 below.
  • the concentration and spray amount of each aqueous solution in 1-36 were determined according to Tables 1-3.
  • Sample 1 and Sample 15 were manufactured by the following steps.
  • a paste-like alkali-containing material was applied to the surface of a concrete block (1 Ocm wide x 20 cm long x 6 cm thick) as a film-forming target (substrate).
  • a concrete block (1 Ocm wide x 20 cm long x 6 cm thick) as a film-forming target (substrate).
  • Sample 1-Sample 11 was made of cement
  • Samples 12 and 13 were made of calcium hydroxide
  • Samples 14 and 15 were made of strontium hydroxide, Each was used.
  • Samples 19 and 12-15 were sprayed with peroxotitanate ion aqueous solution after the cement was dried and solidified, and before samples 10 and 11 were dried.
  • a peroxotitanate ion aqueous solution a mixed solution of a salted titanium aqueous solution and a hydrogen peroxide solution was used for Sample 1 to Sample 4, and a mixed solution of titanium sulfate aqueous solution was used for Samples 5 to 15. Mixed solutions with hydrogen oxide water were used respectively.
  • Samples 3, 11, 13, and 15 were immersed in deionized water.
  • the target sample was immersed in deionized water 1.41 for one day, and then dried.
  • the dipping and drying steps were repeated twice.
  • Sample 16 and Sample 17 were manufactured by the following steps.
  • a paste-like alkali-containing material was applied to the surface of a concrete block (similar to Experimental Example 1) as a film-forming target. As shown in Table 1, cement was used as the alkali-containing material.
  • a soluble titanium salt aqueous solution was attached to the surface of the cement held by the concrete block by spraying.
  • a titanium sulfate aqueous solution was used as the soluble titanium salt aqueous solution.
  • Sample 17 was immersed in deionized water.
  • the target sample was immersed in deionized water 1.41 for one day and then dried.
  • Sample 18 was manufactured by the following steps.
  • a 10 g aqueous solution of peroxotitanate ion was attached to the alkali-containing material as a film-forming target by spraying.
  • 25 g of fly ash was used as the alkali-containing material.
  • This fly ash is an alkaline powder, and has alkali on its surface.
  • Table 1 a mixed solution of a titanium sulfate aqueous solution and a hydrogen peroxide aqueous solution was used as the peroxotitanate ion aqueous solution.
  • Samples 19 to 29 were manufactured by the following steps.
  • the hydrogen peroxide solution was attached to the surface of the concrete block to which the alkaline aqueous solution was attached by spraying.
  • Samples 32 to 36 were manufactured by the following steps.
  • sodium hydroxide, barium hydroxide octahydrate and sodium hydroxide were added to an aqueous solution (aqueous TiOH solution) obtained by adding hydrogen peroxide to a titanium sulfate aqueous solution or a titanium chloride aqueous solution.
  • strontium hydroxide octahydrate was added to produce a pale yellow or white precipitate.
  • the aqueous solution obtained by the above-mentioned mixing was allowed to stand, the supernatant was removed, and 100 ml of water was mixed. Further, this aqueous solution was allowed to stand, the supernatant was removed, and the operation of mixing water was repeated several times. Then, the precipitate was filtered to remove water-soluble components.
  • the obtained precipitate was dried in a desiccator containing silica gel, and then dried in an electric dryer kept at about 107 ° C to obtain Samples 32 to 36.
  • samples 30 and 31 were produced by a conventional film forming method using a titanium-containing gel.
  • An aqueous ammonia solution (NH OH) is added to a mixed aqueous solution of a titanium sulfate aqueous solution and a hydrogen peroxide solution.
  • the suspension was attached to a concrete block (similar to Experimental Example 1) as a film formation target. (3) Immersion in deionized water and drying process
  • a cement was applied to a concrete block (same as in Experimental Example 1), and a titanium oxide film was provided.
  • Sample 1 was set in a measuring container (10 cm long ⁇ 20 cm wide ⁇ 8 cm thick) having an upper surface formed of quartz glass. At this time, the sample 1 was arranged so that the surface (the surface on which the titanium oxide film was formed) faced upward.
  • NO-containing gas nitrogen monoxide
  • first NO-containing gas gas having a volume ratio of 5vol%, N2: 89.5vol%
  • NO: 4.7ppm gas having a volume ratio of 100% Ovol%
  • second NO-containing gas gas having a volume ratio of 100% Ovol%
  • the NO concentration of the exhaust gas from the measurement container for all samples 1 to 31 is determined by the NO concentration of the first NO gas sent to the measurement container ( 4. 7p pm).
  • the NO adsorption speed was determined by the following equation. This NO adsorption rate corresponds to the NO reduction rate when each sample is not irradiated with ultraviolet light.
  • NO adsorption rate molZh Aeration gas flow rate (l'NZh) X (air gas NO concentration-exhaust gas NO concentration) (ppm) /22.4 (l-N / mol)
  • Fig. 1 shows the relationship between the H 2 O ZTi (molar ratio) of the sprayed aqueous solution of peroxotitanate and the NO adsorption rate.
  • Figure 3 shows the NO adsorption rates compared with the types of alkali from the experimental results of Samples 6, 12, 14, 19, and 22.
  • Figure 5 shows the relationship between 2ZTi (molar ratio, the same applies hereinafter) and the NO adsorption rate.
  • Sample 1 was set in a measuring container (10 cm long ⁇ 20 cm wide ⁇ 8 cm thick) having an upper surface formed of quartz glass. At this time, the sample 1 was arranged so that the surface (the surface on which the titanium oxide film was formed) faced upward.
  • the first NO-containing gas was supplied at 0.51 / min from one longitudinal end of the measurement container, and was discharged from the other end. Further, while the first NO-containing gas was ventilated in this way, ultraviolet light was irradiated at a top surface force of 0.6 WZcm 2 as well as a quartz glass force.
  • the NO concentration of the exhaust gas was measured using a chemiluminescence NO concentration measuring device (TN-7: Yanagimoto Seisakusho). Further, the concentration of nitrogen dioxide in the exhaust gas was measured by a detector tube method.
  • TN-7 chemiluminescence NO concentration measuring device
  • NO photooxidation speed molZh Flow rate of ventilation gas (l'NZh) X (NO concentration of exhaust gas-NO concentration of exhaust gas) (ppm) /22.4 (l-N / mol)
  • Table 4 shows the measurement results of X-ray photoelectron spectroscopy.
  • H O ZTi 0.1%
  • H O ZTi 0.1-2
  • the NO photooxidation rates were the same as those of Samples 12, 14, 19, and 22, except for Samples 6 and 7, which used cement as the alkali. Samples 13, 15, 20, and 23, which were immersed in water, showed equivalent or higher values. From this, it is considered that when an alkali other than cement is used, there is no change in properties such that the NO photooxidation rate is significantly reduced by at least immersion in water! /.
  • the NO photoacidification speed was substantially constant.
  • titanium sulfate was used as the soluble titanium salt, the H 2 O ratio increased (that is, H 2 O ZTi increased).
  • H O ZTi at the time of forming the titanium oxide film is 0.1 ⁇ H O Z
  • the NO adsorption rate does not largely depend on the value of Ba (OH) ZTi,
  • the NO photooxidation rate is in the range of 0.25 ⁇ Ba (OH) ZTi,
  • titanium chloride is used as a titanium salt, and calcium hydroxide and strontium hydroxide are used as alkaline earth metal hydroxides. If any one of barium hydroxide is used, chlorine (chlorine compound) can be easily removed only by washing with water.
  • the titanium oxide of the present invention in which the titanium salt is titanium sulfate and the alkaline earth metal hydroxide is any one of calcium hydroxide, strontium hydroxide, and barium hydroxide
  • the film forming method calcium sulfate, strontium sulfate, or barium sulfate is generated when titanium oxide is generated.
  • the calcium sulfate, sodium sulfate, or barium sulfate functions as a binder for titanium oxide (titanium dioxide) with almost no reduction in the photocatalytic ability of the titanium oxide film.
  • titanium oxide titanium oxide of the present invention in which the titanium salt is titanium sulfate and the alkaline earth metal hydroxide is any one of calcium hydroxide, strontium hydroxide, and barium hydroxide
  • the non-crystalline component is a photocatalytic component that is active in NO photooxidation.
  • the atomic ratio of the remaining oxygen to titanium was calculated to be almost 2 (Ti: 0 ⁇ 1: 2), assuming that 3 exists. From this, it is presumed that titanium exists as titanium dioxide (TiO 2).
  • Ti (SO) HO -Ba (OH) system titanium, oxygen, barium,
  • titanium exists as titanium dioxide (TiO 2)
  • the method of forming a titanium oxide film of the present invention shows that amorphous titanium dioxide (amorphous titanium dioxide) is used. Is generated, which can be inferred to be a photocatalytic component that is active in NO photooxidation. That is, according to the method for forming a titanium oxide film of the present invention, a titanium oxide film containing amorphous titanium dioxide as a photocatalytic component can be formed. In addition, carbonate and barium sulfate coexist in these precipitates. However, the photocatalytic activity of the amorphous dioxide titanium is determined by these coexisting substances.
  • the titanium salt is titanium sulfate and the alkaline earth metal hydroxide is any one of calcium hydroxide, strontium hydroxide, and barium hydroxide. According to this, calcium sulfate, strontium sulfate, or barium sulfate is produced when titanium oxide is produced.
  • the calcium sulfate, strontium sulfate, or barium sulfate functions as a binder for titanium oxide (titanium dioxide) without substantially reducing the photocatalytic ability of the titanium oxide film. This makes it possible to form a more durable oxidized titanium film which is hardly eluted.
  • Example 2 is an example for demonstrating that an oxidized titanium film having a photocatalytic function is formed even when the timing of applying an alkali is changed. Is not limited to the following examples.
  • the concrete block with the titanium oxide film formed on the surface was placed in an open-topped container (length 10 cm x width 20 cm x thickness 8 cm), and the top surface was covered with quartz glass. .
  • a gas containing NO (0.95 ppm, O: 10.5%, N: 89.5%) containing NO is ventilated from one end of the container in the longitudinal direction (1 L NZmin: NO aeration).
  • the gas was taken out from the other end in the longitudinal direction of the container, and the NO concentration was measured by a NO concentration measuring device by a chemiluminescence method.
  • the NO concentration at the container outlet was lower than the NO concentration at the container inlet (NO: 0.95 ppm). This was considered to be due to NO adsorption, and the NO adsorption rate was determined by the following equation. Table 5 shows the results.
  • NO adsorption rate molZh gas flow rate (1 NZh) X (concentration of NO at inlet of vessel-NO concentration at outlet of vessel) (ppm) / 22.4 (1-N / mol)
  • the sample sprayed (Test 201) and the sample sprayed with an aqueous solution of barium hydroxide (Test 203) show a NO adsorption rate of 0.18 and 0.16 / z molZh, respectively, and may have NO adsorption performance. all right.
  • NO photooxidation rate molZh gas flow rate (1 NZh) X (concentration of NO at inlet of vessel-NO concentration at outlet of vessel) (ppm) / 22.4 (1-N / mol)
  • the block on which the titanium oxide film formed as described above was formed was immersed in water (deionized water, 1.41) all day and night, and dried.
  • the oxidation rate was determined (tests 202 and 204).
  • the NO adsorption rate of the concrete block was 0.08 and 0.08 ⁇ mol / h, and the NO photooxidation rate was 0.59 and 0.66 ⁇ mol / h, respectively. Although both the adsorption speed and the NO photoacidification speed were lower than before the water immersion, it was clear that the NO adsorption performance and the NO photoacidification performance remained.
  • the block on which the titanium oxide film was formed was immersed in water in the same manner as in Experimental Examples 201 to 204 (Tests 206 and 208).
  • Table 5 shows the results of measurement of the NO adsorption rate and the NO photooxidation rate before water immersion (Tests 205 and 207) and after water immersion (Tests 206 and 208).
  • the NO adsorption rates of the samples (Tests 205 and 207) before water immersion were 0.19 and 0.16 11101711, respectively.
  • the ⁇ 0 photo-oxidation rates were 1.18 and 0. 0 molZh, respectively, indicating that both have NO adsorption performance and NO photooxidation performance.
  • these samples were immersed in water (deionized water) for 24 hours, and then dried (tests 206 and 208).
  • the NO adsorption rates were 0.05 and 0.06 / z molZh, respectively, The velocities were 0.23 and 0.35 molZh, respectively, indicating that both the NO adsorption performance and the NO photooxidation performance remained.
  • the decrease in the NO adsorption speed and the NO photooxidation speed after water immersion in this case is larger than the decrease in the NO adsorption speed and NO photooxidation speed after water immersion in Experimental Examples 201-204. ing. This is presumed to be due to the fact that the rate at which part of the titanium oxide held on the surface of the concrete block during the water immersion dropped off was large.

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Abstract

La présente invention concerne un procédé de production d'oxyde de titane qui consiste à faire réagir un ion peroxotitanate qui peut être dérivé d'un produit de réaction d'une solution de sel de titane aqueux et de peroxyde d'hydrogène, en présence d'un alcalin. Cette réaction peut être utilisée pour former un film d'oxyde de titane sur un article revêtu de ce film. Par exemple, une solution aqueuse de ion peroxotitanate (par exemple Ti(SO4)2aq + H2O2) attaché à un article de façon à posséder un film possédant un alcalin sur sa surface (par exemple un produit de ciment) par pulvérisation, application ou immersion de façon à former ainsi un film d'oxyde de titane. Cet alcalin peut provenir d'une solution alcaline aqueuse dont le but est d'être présente sur la surface par pulvérisation, application ou immersion. La surface comprend de préférence un matériau poreux. Ce procédé permet de former un film d'oxyde de titane possédant des particules d'oxyde de titane hautement dispersées, ce qui entraîne la réduction de la quantité d'oxyde de titane à utiliser et, permet aussi de former un film d'oxyde de titane au moyen d'un processus simple et facile, ce qui entraîne la réduction des coûts de production requis pour former un film d'oxyde de titane.
PCT/JP2004/016231 2003-12-02 2004-11-01 Procede de production d'oxyde de titane, melange actif par photocatalyse, procede de fabrication de film d'oxyde de titane utilisant ces elements, procede de production d'article revetu d'oxyde de titane et article revetu d'oxyde de titane fabrique au moyen de ces elements et solution de fabrication de film d'oxyde de titan WO2005054135A1 (fr)

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JP2005515886A JP4680064B2 (ja) 2003-12-02 2004-11-01 酸化チタンの製造方法、光触媒活性混合物、それらを利用した酸化チタン膜の成膜方法、酸化チタン被覆体の製造方法、及びそれらにより得られた酸化チタン被覆体、並びにそれに用いる酸化チタン成膜用溶液

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Cited By (2)

* Cited by examiner, † Cited by third party
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CZ300950B6 (cs) * 2007-09-12 2009-09-23 Ústav anorganické chemie AV CR, v.v.i. Zpusob výroby fotokatalytických pigmentu
CZ301006B6 (cs) * 2008-03-07 2009-10-14 Ústav anorganické chemie AV CR, v. v. i. Zpusob výroby fotokatalyticky aktivního monodisperzního oxidu titanicitého

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JP6706615B2 (ja) * 2015-06-02 2020-06-10 東邦チタニウム株式会社 チタン酸アルカリおよび摩擦材
CN105498744A (zh) * 2016-01-27 2016-04-20 北京富莱士博科技发展有限公司 高活性纳米CaCO3-TiO2复合光催化材料的制备方法
CN107051549B (zh) * 2017-03-21 2019-06-25 重庆大学 双异质结构光催化剂及其应用和制备方法
CN107469554A (zh) * 2017-08-22 2017-12-15 海宁滴滴箱包智能科技有限公司 一种负载二氧化硅/二氧化钛复合微球的除甲醛复合纤维材料的制备方法
CN114351235B (zh) * 2022-02-14 2023-02-28 淮阴工学院 一种镍钛合金表面无Ni功能微孔结构的制备方法

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JPH0971418A (ja) * 1995-08-31 1997-03-18 Saga Pref Gov チタニア膜形成法
JPH09221324A (ja) * 1996-02-09 1997-08-26 Nippon Parkerizing Co Ltd 酸化チタン系セラミック塗料およびその製造方法
JP2000247639A (ja) * 1999-02-26 2000-09-12 Saga Prefecture チタン酸化物形成用溶液の製造方法

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CN1247462C (zh) * 2003-08-05 2006-03-29 拉萨绿能科技实业有限公司 制备锐钛型纳米二氧化钛的工艺

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JPH0971418A (ja) * 1995-08-31 1997-03-18 Saga Pref Gov チタニア膜形成法
JPH09221324A (ja) * 1996-02-09 1997-08-26 Nippon Parkerizing Co Ltd 酸化チタン系セラミック塗料およびその製造方法
JP2000247639A (ja) * 1999-02-26 2000-09-12 Saga Prefecture チタン酸化物形成用溶液の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ300950B6 (cs) * 2007-09-12 2009-09-23 Ústav anorganické chemie AV CR, v.v.i. Zpusob výroby fotokatalytických pigmentu
CZ301006B6 (cs) * 2008-03-07 2009-10-14 Ústav anorganické chemie AV CR, v. v. i. Zpusob výroby fotokatalyticky aktivního monodisperzního oxidu titanicitého

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